Epoxides containing a perfluorovinyl group

ABSTRACT

Epoxides containing a perfluorovinyl group, and polymers made therefrom by polymerization of the epoxy function are disclosed. Such epoxides form polymers and copolymers useful for coatings, adhesion control agents, surface modifiers and crosslinking agents.

This is a division of application Ser. No. 08/243,428 filed May 16,1994, now U.S. Pat. No. 5,914,412.

FIELD OF INVENTION

Epoxides containing a perfluorovinyl group, and polymers made therefromby polymerization of the epoxy group, are provided.

BACKGROUND OF THE INVENTION

U.S. Pat. Nos. 4,544,720 and 4,581,412 disclose compounds of the formulaCF₂ ═Cr--(--CF₂ --)--_(m) --(--CH₂ --)--_(n) X, wherein m is 0 or aninteger of 1-10, n is 0 or an integer of 1-4, and (most pertinently) Xis ##STR1##

In the case where m is 0 and n is 2, 3 or 4, these disclosed compoundsare identical to those described in this application. The only examplein these patents of these compounds made is where m is 0 and n is 1. Thechemistry described for this synthesis in the specification of thesepatents (in '720 at col. 3, lines 55 to end; in '412 at col. 3, line 61to col. 4, line 8), uses the addition of allyl alcohol to aperhalogenated-alkyl iodide, which will only produce the compound wheren is 1. Chemistry is described (in '720 at col. 3, lines 43-49; in '412at col. 3, lines 36-44), but not done, for the preparation of otherepoxides, including those described in this application. However, thepreparation of the starting material for that synthesis is neitherdescribed nor is a reference given. Therefore, although the instantcompounds are mentioned, ore of ordinary skill in the art would not beable to make them from disclosures in these patents.

It is the object of this invention to provide epoxides containing aperfluorovinyl group, may be polymerized through either the vinyl group(see U.S. Pat. Nos. 4,544,720 and 4,581,412) or through the epoxy group(infra). It is a further object of this invention to provide polymersand copolymers made from these epoxide compounds by polymerization ofthe epoxy group.

SUMMARY OF THE INVENTION

Epoxides containing a perfluorovinyl group, and polymers made therefromby polymerization of the epoxy function are disclosed. The epoxides areof the formula ##STR2## wherein n is an integer of 2 through 10.

Such epoxides may be polymerized through either the epoxy or vinylfunctionality to form polymers useful for coatings, adhesion controlagents, surface modifiers and crosslinking agents. Polymers of thestructure ##STR3## wherein n is an integer from 2 through 10 are alsodisclosed.

DETAILS OF THE INVENTION

This invention concerns a compound of the formula ##STR4## wherein n isan integer of 2 through 10.

In these compounds, herein sometimes termed epoxides containing aperfluorovinyl group, it is preferred if n is 2, 4 or 6.

The epoxides are made by the selective epoxidation of the correspondingdiene, using a combination of fluorine, water and acetonitrile. Suchprocedures are found in S. Rozen and M. Brand, Angew. Chem. Int. Ed.,vol. 25, pp. 554-555 (1986) and commonly assigned U.S. patentapplication Ser. No. 420,454, filed Oct. 12, 1989, both of which arehereby included by reference. Further illustration of the epoxidation isfound in the Examples.

The dienes that are epoxidized can be made by methods found in commonlyassigned U.S. patent applications Ser. No. 450,257, filed Dec. 13, 1989,and 530,638, now U.S. Pat. Nos. 5,015,790 and 5,043,490 repectively, thelatter of which is filed herewith, and both of which are included hereinby reference. Specific illustrations will be found in the Examples.

The epoxides containing a perfluorovinyl group are useful as monomers,see below and U.S. Pat. Nos. 4,544,720 and 4,581,412.

Also contemplated by this invention are a polymer, comprising, units ofthe formula ##STR5## wherein n is an integer from 2 through 10.

In preferred polymers n is 2, 4 or 6, and in especially preferredpolymers, n is 4. It is also preferred if the polymer consistsessentially of the units ##STR6## in other words is a homocolymer.

In another preferred embodiment it is preferred if the polymer furthercomprises units of the formula --O--CH₂ --CH₂ -- and/or units of theformula ##STR7## in other words, copolymers with ethylene oxide and/orpropylene oxide, respectively. By the term homopolymer above is meantthat only one or more epoxides containing a perfluorovinyl group areused as monomers to make the homopolymer. Homopolymers and copolymersmav include variations such as head to head, tail to tail and head totail sequences.

Polymers from these monomers have been made (see U.S. Pat. Nos.4,544,720 and 4,581,412), but these polymers have been made bypolyme-ization of the vinyl group. The instant polymers can be made byan acid catalyzed polymerization of the epoxy group, see for exampleBritish Patent 782,615, which is hereby included by reference, fortypical procedures. Specific polymerizations are illustrated in theExamples.

It has been found that compounds wherein n=4 polymerize exceptionallyeasily, and the monomeric epoxide containing a fluorovinyl group must bestored at about 0° C. or less to prevent polymerization. Note in Example4 that the polymerization is done thermally in the absence of catalyst.

EXPERIMENTAL PROCEDURES General Procedure for Working with Fluorine

Fluorine is a strong oxidizer and a very corrosive material. Anappropriate vacuum line made from copper or Monel® in a well ventilatedarea should be constructed for working with this element. The reactionsthemselyes can be carried out in glass vessels. If elementaryprecautions are taken, work with fluorine is relatively simple.

General Procedure for Producing the Oxidizing Reaent

Mixtures of 10%-15% F₂ diluted with nitrogen are used in this work. Thegas mixtures are prepared in a secondary container before the reactionis started. This mixture is then passed in a rate of about 400 ml perminute through a cold (-10° C.) and vigorously stirred mixture of 400 mlCH₃ CN and 40 ml H₂ O. The formation of the oxidizing power is monitoredby reacting aliquots with acidic aqueous solution of KI. The liberatediodine is then titrated with thiosulfate. Concentrations of more then amol/liter oxidizing reagent can be reached.

General Epoxidation Procedure

An appropriate amount of olefin (see discussion) is dissolyed in about50 ml of CH₂ Cl₂ cooled to 0° C. and added in one portion to thereaction vessel in which the oxidizing agent has been preared. Thetemperature and the time of the reaction depends on the individualolefin. After the reaction is completed, the reaction mixture isneutralized with saturated sodium bicarbonate solution. The reactionmixture is then poured into 1.5 liter of water, extracted with CFCl₃ andwashed with NaHCO₃ and water until neutral. The organic layer is driedover MgSO₄, and the solyent distilled under reduced pressure, preferablyat room temperature. The crude product is usually distilled underreduced pressure.

EXAMPLE 1 Epoxidation of 1,1,2-Trifluoro-1,5-Hexadiene

200 mmols of the oxidizing solution were made. To this solution 9.5 g(70 mmol) of the olefin dissolved in 30 ml CH₂ Cl₂ were added. After 2minutes at 0° C. the reaction was worked up as described above. Afterthe distillation of the solvent the reaction mixture was distilled andthe main fraction which was identified as5,6-epoxy-1,1,2-trifluoro-1-hexene with a bp=58° C./30 mm, yield 60%;IR=1200, 1300 cm⁻¹ ; ¹ H NMR=3.32 (m, 1H), 2.94 (m, 1H), 2.84 (m, 1H),2.50 (m, 1H), 2.23 (m, 1H), 2.00 (m, 2H), ¹⁹ F NMR=-101.6, 102.7 (2s,br, 1F), -116.7, -117.8 (2m, 1F), -169.2 (m, br, 1F); MS m/e=151([M-1]⁺), Calc mass for C₆ H₆ F₃ O=151.0371; Found: 151.0367.

In this case the only effect of lowering the ratio of theoxidizer/reactant as well as the temaerature, was lowering theconversion of the starting material from quantitative to 70%.

EXAMPLE 2 Epoxidation of 1,1,2-Trifluoro-1,7-Octadiene

160 mmols of tne oxidizing solution were made and cooled to -40° C. Tothis solution 9.7 a (60 mmol) of the olefin dissolyed in 30 ml CH₂ Cl₂were added also after cooling to -40° C. After 2 minutes the reactionwas worked up as described above. After the distillation of the solventthe reaction mixture was distilled and the main fraction identified as7,8-epoxy-1,1,2-trifluoro-1-octene with a bp=50-59° C./7 mm, yield 50%;¹ H NMR=2.92 (m, br, 1H), 2.78 (t, J=4.2 Hz, 1H), 2.48 (m, 1H), 2.36 (m,1H), 2.28 (m, 1H), 1.56 (m, 6H); ¹⁹ F NMR=-105.9, -106.1, -106.4, -106.6(4s, br, 1F), -124.9, -125.4, -125.5, -125.0 (4t, J=4.1 Hz, 1F), -174.6,-175.2 (dm, J=82.9 Hz, 1F); MS m/e=162 (M⁺), 108 ([CF₂ ═CFCH₂ CH₂ -1]⁺),95 ([CF₂ ═CFCH_(2]) ⁺).

EXAMPLE 3 Epoxidation of 1,1,2-Trifluoro-1,9-Decadiene

65 mmols of the oxidizing solution were made. To this solution 5 g (26mmol) of the olefin dissolved in 20 ml CH₂ Cl₂ were added at -10° C.After 10 minutes the reaction was worked up as described above. Afterthe distillation of the solvent the reaction mixture consisted of 19%starting material and 55% of 9,10-epoxy-1,1,2-trifluoro-1-decene; ¹ HNMR=2.95 (m, 1H), 2.78 (t, J=4 Hz, 1H), 2.46 (q, J₁ =6 Hz, J₂ =4 Hz,1H), 1.3-2.4 ppm (m, 12H); ¹⁹ F NMR=-106.5 (m, 1F), -125.7 (m, 1F),-175.1 (m, 1F); MS m/e=207 ([M-1]⁺), Calc mass for C₁₀ H₁₄ F₃O=207.0997; Found: 207.1029; 95 ([CF₂ ═CFCH₂ ]⁺).

EXAMPLE 4 Polymerization of 7,8-Epoxy-1,1,2-Trifluoro-1-Octene

Cooled 7,8-epoxy-1,1,2-trifluoro-1-octene (1.0 g) was placed in a driedflask. The temperature was raised to 25 to 30° C. and the neat substratewas stirred at this temperature for 10 days. The resulting viscousproduct was dissolved in an acetone (15 ml) and conc. HCl (0.5 ml)mixture with stirring. Water was added and the insoluble polymer laverwas separated. This washing process was repeated for 2-3 times, thepolymer isolated and was dried in which vacuum in desiccator. Afterdrying, 100% yield of polymer was obtained with a weight averagemolecular weight of 32,200. F-19 NMR indicated that the polymerizationwas occurred on the epoxde exclusively, the CF₂ ═CF-- was not involvedin the polymerization. F-19 NMR (CDCl₃): -106.6 (dm, 1F), -125.6(tm,1F), -174.8 (dm, 1F); H-1 NMR (CDCl₃): δ 3.50 (br, 3H), 2.30 (d, br,2H), 1.50 (br, 6H).

EXAMPLE 5 Polymerization of 5,6-Epoxy-1,1,2-Trifluoro-1-Hexene

In a dried flask was charged 5,6-epoxy-1,1,2-trifluoro-1-hexene (0.912g) and aluminum chloride initiator (13.5 mg). The polymerizationproceeded at 85° C. for 24 hours. The resulting polymer was worked up asdescribed in Example 4. 0.46 g of brown solid polymer was obtained witha Tg 24.7° C. This polymer has a weight average molecular weight of10,900. The polymer structure was supported by its H-1 and F-19 NMRspectra.

EXPERIMENT 1 Preparation of 1,1,2-Trifluoro-1,6-Hexadiene CF₂═CF--I+xs.CH₂ ═CH₂ →CF₂ ═CF--CH₂ CH₂ CH₂ CH₂ I

In a 1400 ml HC Shaker tube was charged iodotrifluoroethylene (71.3 g,0.343 mole) and d-limonene (1.7 g). The tube was sealed, cooled andevacuated, and ethylene gas (240 g, 8.57 mole) was transferred into thetube. The tube was agitated and heated slowly to 200° C., then was keptat this temperature for 24 hrs. The product unloaded from the tube waspurified by distillation. 61.0 g (67.4% yield) of1,1,2-trifluoro-6-iodo-1-hexene was obtained as a clear licuid, Bp: 58°C./2.5 mm. ¹ H NMR (CDCl₃): δ 3.22 (m, 2H), 2.02 to 2.60 (m, 6H); F-19NMR (CDCl₃): -103.5, -104.6 (2s, br, 1F), -114.7, -115.8 (2s, br, 1F),-164.1 (s, br, 1F).

CF₂ ═--CH₂ CH₂ CH₂ CH₂ I→CF₂ ═CF--CH₂ CH₂ CH═CH₂

1,1,2-Trifluoro-6-iodo-1-hexene (52.8 g, 0.2 mole) obtained from abovewas mixed with 10 M KOH aqueous solution (125 ml, 1.25 mole) andbenzyldodecyl bis(2-hydroxypropyl)ammonium chloride (14.4 g, 60 wt. %aqueous solution, 0.02 mole) and was stirred for 24 hrs at roomtemperature. The too organic layer was then separated, washed withwater, and distilled to give the title product, 20 g (73.5% yield), as aclear colorless liquid. Bp: 50° C./200 mm. ¹ H NMR (CDCl₃): δ 6.00 (m,1H), 5.52 (m, 2H), 2.54 (m, 1H), 2.30 (m, 1H), 2.20 (m, 2H); F-19 NMR(CDCl₃): -100.8, -101.9 (2m, 1F), -115.4, -116.5 (2m, 1F), -161.8 (m,1F).

EXPERIMENT 2 Preparation of 1,1,2-Trifluoro-1,8-Octadiene ClCF₂CFClI+CH₂ ═CH--CH₂ CH₂ --CH═CH₂ →ClCF₂ CF₂ CFClCH₂ CHI--CH₂ CH₂ --CH═CH₂

Sodium hydrosulfite (88%, 10 g, 0.05 mole), sodium bicarbonate (3.7 g,0.05 mole) and acetonitrile (20 ml) were mixed at 40° C. with stirring.A solution of ClCF₂ CFClI (56 g, 0.2 mole) and 1,5-hexadiene (33 g, 0.4mole) was added. The reaction temperature was controlled at around 60°C. during the addition and was stirred for 1 hr at 60° C. after theaddition was complete. The lower organic layer was separated anddistilled to give the desired olefin product (35 g, 48% yield) as aclear licuid. Bp. 124-128° C./30 mm.

ClCF₂ CFClCH₂ CHI--CH₂ CH₂ --CH═CH₂ →ClCF₂ CFCl--(CH₂)₄ --CH═CH₂

5-Iodo-7,8-dichloro-7,8,8-trifluoro-1-octene compound (36 g, 0.1 mole)from above in absolute ethanol (30 ml) was added slowly into asuspension of Zn (22 g, 0.3 mole)/EtOH (50 ml). An exothermic reactionwas observed. The reaction mixture was refluxed for 1 hr after all thesubstrate was added. The mixture was poured into a dil. HCl/ice watermixture, and the bottom laver was separated, dried over MgSO₄. Thefraction boiling at 88-90° C./15 mm was collected to give the desiredproduct (14 g, 59% yield).

ClCF₂ CFCl--(CH₂)₄ --CH═CH₂ →CF₂ ═CF--(CH₂)₄ --CH═CH₂

7,8-Dichloro-7,8,8-trifluoro-1-octene (23.7 g, 0.1 mole), Zn-dust (19.5g, 0.3 mole) and DMSO solvent (50 ml) were mixed and was heated at140-180° C. The distillate, which boiled at 120-140° C., was collected.The reaction was continued for about 4 hrs until no more product wasdistilled over. The distillate was washed with cold water, dried overNa₂ S₂ O₄ and distilled again to give the pure diolefin product (11 g,66% yield) as a clear liquid. Bp. 118-120° C. ¹ H NMR (CDCl₃): 5.68 (m,1H), 5.00 (d, 1H), 4.88 (s, 1H), 1.80-2.50 (m, 4H), 1.00-1.80 (m, 4H);F-19 NMR (CDCl₃): -105.5 (dd, 1F), -124.6 (dd, 1F), -174.7 (dm, 1F); IR:1640 cm⁻¹, 1794 cm⁻³.

CF₂ ═CF--(CH₂)₆ --CH═CH₂ was synthesized similarly, Bp. 74-76° C./40 mm.¹ H NMR (CDCl₃): 5.70 (m, 1H), 5.00 (dm, 1H), 4.82 (m, 1H), 1.80-2.50(m, 4H), 0.80-1.80 (m, 8H); F-19 NMR (CDCl₃): -105.4 (dd, 1F), -124.5(dd, 1F), -173.5 (dm, 1F); IR: 1640 cm⁻¹, 1795 cm⁻¹.

Although preferred embodiments of the invention have been describedhereinabove, it is to be understood that there is no intention to limitthe invention to the precise constructions herein disclosed, and it isto be further understood that the right is reserved to all changescoming within the scoce of the invention as defined by the appendedclaims.

We claim:
 1. A polymer, comprising, units of the formula ##STR8##wherein n is an integer from 2 through
 10. 2. The polymer as recited inclaim 1 wherein said n is 2, 4 or
 6. 3. The polymer as recited in claim2 wherein said n is
 4. 4. The polymer as recited in claim 1 that is ahomopolymer.
 5. The polymer as recited in claim 1 which is a copolymerwith ethylene oxide and/or propylene oxide.
 6. The polymer as recited inclaim 5 which is a copolymer with ethylene oxide.
 7. The polymer asrecited in claim 5 which is a copolymer with propylene oxide.
 8. Thepolymer as recited in claim 2 which is a copolymer with ethylene oxideand/or propylene oxide.
 9. The polymer as recited in claim 8 which is acopolymer with ethylene oxide.
 10. The polymer as recited in claim 8which is a copolymer with propylene oxide.